(2R,3S,4R,5R)-3,4-dibenzyloxy-N-tert-butyloxycarbonyl-2-tert-butyldiphenylsilyloxymethylpyrrolidine | 1006295-21-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3S,4R,5R)-3,4-dibenzyloxy-N-tert-butyloxycarbonyl-2-tert-butyldiphenylsilyloxymethylpyrrolidine
• 英文别名: (2R,3S,4R,5R)-3,4-bis(benzyloxy)-N-(tert-butyloxycarbonyl)-2'-O-(tert-butyldiphenylsilyl)-2,5-bis(hydroxymethyl)pyrrolidine；tert-butyl (2R,3S,4R,5R)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-5-(hydroxymethyl)-3,4-bis(phenylmethoxy)pyrrolidine-1-carboxylate
• CAS: 1006295-21-1
• 化学式: C₄₁H₅₁NO₆Si
• 分子量: 681.945
• InChiKey: BAQNVUFNCNUBLS-KMJUKGKLSA-N

物化性质

• 沸点：
  706.0±60.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.71
• 重原子数：
  49
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  77.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2R,3S,4R,5R)-3,4-dibenzyloxy-N-tert-butyloxycarbonyl-2-tert-butyldiphenylsilyloxymethylpyrrolidine 在 咪唑 、 碘 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 以83%的产率得到(2R,3S,4R,5S)-3,4-bis(benzyloxy)-1-(tert-butoxycarbonyl)-2-[(tert-butyldiphenylsilyloxy)methyl]-5-(iodomethyl)pyrrolidine
  参考文献：
  名称：

  Polyhydroxylated Pyrrolidines: Synthesis of Trideoxy-2,5-iminohexitols

  摘要：

  利用以前从商用 d-果糖中制备的三正对映体保护的吡咯烷作为同手性起始原料，合成了一系列天然存在的吡咯烷生物碱和类似物，其一般结构为三脱氧-2,5-亚氨基己糖醇（亚氨基或氮杂杉糖）。其中一些化合物对糖苷酶和糖基转移酶具有抑制活性，因此具有潜在的治疗作用。

  DOI：

  10.1055/s-2008-1072566
• 作为产物：
  描述：

  (2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine 、 三甲基乙酸酐 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到(2R,3S,4R,5R)-3,4-dibenzyloxy-N-tert-butyloxycarbonyl-2-tert-butyldiphenylsilyloxymethylpyrrolidine
  参考文献：
  名称：

  Total synthesis of natural (+)-hyacinthacine A6 and non-natural (+)-7a-epi-hyacinthacine A1 and (+)-5,7a-diepi-hyacinthacine A6

  摘要：

  Naturally occurring (1S,2R,3R,5R,7aR)-1,2-dihydroxy-3-hydroxymethyl-5-methylpyrrolizidine [(+)-hyacinthacine A(6), 2] together with unnatural (1S,2R,3R,7aS)-1,2-dihydroxy-3-hydroxy-methylpyrrolizidine [(+)-7a-epi-hyacinthacine A(1), 3] and (1S,2R,3R,5S,7aS)-1,2-dihydroxy-3-hydroxy-methyl-5-methylpyrrolizidine [(+)-5,7a-diepi-hyacinthacine A(6), 4] have been synthesized from a DALDP derivative [5, (2R,35,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)-pyrrolidine], as the homochiral starting material. The synthetic process employed took advantages of Wittig methodology followed by internal lactamization, in the case of (+)-7a-epi-hyacinthacine A(1) (3), and reductive amination for (+)-hyacinthacine A(6) (2) and (+)-5,7a-diepi-hyacinthacine A(6) (4). (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.03.049

文献信息

• Lipase-mediated synthesis of enantiomeric 2,5,6-trideoxy-2,5-iminohexitols
  作者：Isidoro Izquierdo、María T. Plaza、Juan A. Tamayo、Francisco Franco、Fernando Sánchez-Cantalejo

  DOI：10.1016/j.tet.2008.03.089

  日期：2008.5

  Syntheses of 2,5,6-trideoxy-2,5-imino-d-alditol (2, 6-deoxy-DADP) and its enantiomer (3) from tri-orthogonally protected derivatives of DADP have been developed employing lipase-mediated kinetic desymmetrization and protecting group manipulations. Thus, and as an example, the starting DADP derivative (4) was transformed into a new symmetrical 2,5-bis(hydroxymethyl)pyrrolidine (6) by sequential N-protection

  2,5,6-三脱氧-2,5-亚氨基d-糖醇（的合成2，6-脱氧DADP）及其对映体（3从DADP的三正交保护的衍生物）已经开发了采用脂肪酶介导的动力学非对称化和保护组操作。因此，并且作为实例，通过顺序的N-保护和双-O-去甲硅烷基化，将起始DADP衍生物（4）转化为新的对称的2,5-双（羟甲基）吡咯烷（6）。最好在乙酰化条件下进行脂肪酶介导的6脱对称，得到（2 R）-乙酰氧基甲基衍生物7。绝对配置和ee为7通过与同手性样品的化学相关性明确建立了它们。化合物7直接转化为目标2,5,6-三苯氧基-2,5-亚氨基己糖醇3。
• A New Synthetic Approach to (+)-Hyacinthacine A₁and the First Total Synthesis and Absolute Configuration Assignment of Naturally Occurring (+)-Hyacinthacine A₆
  作者：Isidoro Izquierdo、María T. Plaza、Juan A. Tamayo、Fernando Sánchez-Cantalejo

  DOI：10.1002/ejoc.200700820

  日期：2007.12

  Naturally occurring (1S,2R,3R,7aR)-1,2-dihydroxy-3-hydroxymethylpyrrolizidine [(+)-hyacinthacine A1 (1)] and(1S,2R,3R,5R,7aR)-1,2-dihydroxy-3-hydroxymethyl-5-methylpyrrolizidine [(+)-hyacinthacine A6 (2)] have been synthesized by Wittig's methodology using aldehyde 7, prepared from (2R,3S,4R,5R)-3,4-bis(benzyloxy)-2′-O-(tert-butyldiphenylsilyl)-2,5-bis(hydroxymethyl)pyrrolidine (3, partially protected

  天然存在的 (1S,2R,3R,7aR)-1,2-dihydroxy-3-hydroxymethylpyrrolizidine [(+)-hyacinthacine A1 (1)] 和 (1S,2R,3R,5R,7aR)-1,2-dihydroxy -3-羟甲基-5-甲基吡咯里西啶 [(+)-hyacinthacine A6 (2)] 已通过 Wittig 的方法合成，使用醛 7，由 (2R,3S,4R,5R)-3,4-bis(benzyloxy)-制备2'-O-（叔丁基二苯基甲硅烷基）-2,5-双（羟甲基）吡咯烷（3，部分保护的 DALDP），作为同手性原料和适当的叶立德，得到相应的 α,β-不饱和酯 8 或酮9分别进行内酰胺化和还原胺化，得到相应的中间体pyrrolizidin-5-one 11和完全保护的吡咯里西啶14。化合物11和14分别很容易转化为上述风信子1和2。(© Wiley-VCH
• Total synthesis of natural (+)-hyacinthacine A6 and non-natural (+)-7a-epi-hyacinthacine A1 and (+)-5,7a-diepi-hyacinthacine A6
  作者：Isidoro Izquierdo、María T. Plaza、Juan A. Tamayo、Francisco Franco、Fernando Sánchez-Cantalejo

  DOI：10.1016/j.tet.2010.03.049

  日期：2010.5

  Naturally occurring (1S,2R,3R,5R,7aR)-1,2-dihydroxy-3-hydroxymethyl-5-methylpyrrolizidine [(+)-hyacinthacine A(6), 2] together with unnatural (1S,2R,3R,7aS)-1,2-dihydroxy-3-hydroxy-methylpyrrolizidine [(+)-7a-epi-hyacinthacine A(1), 3] and (1S,2R,3R,5S,7aS)-1,2-dihydroxy-3-hydroxy-methyl-5-methylpyrrolizidine [(+)-5,7a-diepi-hyacinthacine A(6), 4] have been synthesized from a DALDP derivative [5, (2R,35,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)-pyrrolidine], as the homochiral starting material. The synthetic process employed took advantages of Wittig methodology followed by internal lactamization, in the case of (+)-7a-epi-hyacinthacine A(1) (3), and reductive amination for (+)-hyacinthacine A(6) (2) and (+)-5,7a-diepi-hyacinthacine A(6) (4). (C) 2010 Elsevier Ltd. All rights reserved.
• Polyhydroxylated Pyrrolidines: Synthesis of Trideoxy-2,5-iminohexitols
  作者：Isidoro Izquierdo、María Plaza、Juan Tamayo、Daniele Lo Re、Fernando Sánchez-Cantalejo

  DOI：10.1055/s-2008-1072566

  日期：2008.5

  A series of naturally occurring pyrrolidine alkaloids and analogues, with the general structure of trideoxy-2,5-iminohexitols (imino- or azasugars), have been enantiosynthesized using triorthogonally protected pyrrolidines, previously prepared from commercial d-fructose, as homochiral starting materials. The inhibitory activity of some of the described compounds against glycosidases and glycosyltransferases makes them potential therapeutic agents.

  利用以前从商用 d-果糖中制备的三正对映体保护的吡咯烷作为同手性起始原料，合成了一系列天然存在的吡咯烷生物碱和类似物，其一般结构为三脱氧-2,5-亚氨基己糖醇（亚氨基或氮杂杉糖）。其中一些化合物对糖苷酶和糖基转移酶具有抑制活性，因此具有潜在的治疗作用。